MXPA96004645A - Plastic compositions pigmenta - Google Patents

Abstract

The present invention relates to a plastic composition comprising a high molecular weight material, and an effective coloring amount of an azo pigment of the formula: wherein M is Mg, Ca, Sr, Ba or Mn or a mixture of two or more of them, R1 and R2 are chlorine or methyl, x is zero1, and is zero1 and the sum of x and y is 1, provided that, when the high molecular weight material is polyvinyl chloride, and it is

Description

PIGMENTED PLASTTCO COMPOSITIONS This invention relates to pigmented plastic composites, to novel azo pigments suitable for use in these compositions, and to their production. It has been discovered that certain azo pigments have very good stability at high temperature when used as pigment plastics. According to the above, in one aspect the present invention provides a plastic composition comprising a high molecular weight material and an azo pigment of the formula: wherein M is Mg, Ca, Sr, Ba or Mn or a mixture of two or more thereof. Rl and R2 are chlorine or methyl, x is zero or 1, and is zero or 1 and the sum of x and y is 1. with the proviso that, when the high molecular weight material is polyvinyl chloride. and it is zero.

In the especially preferred compositions of the invention, the pigment is of the formula I wherein M is Ca, x is 1 e and is zero, or of the formula I wherein M is Ca, y is 1, and x is zero. The pigments of the formula I wherein R1 and R2 are each methyl, x is 1, and y is zero, are believed to be novel. A pigment of formula I is also believed to be novel where M is Ca, x is zero, and y is 1, in an orange crystalline form exhibiting an X-ray diffraction pattern having six prominent X-ray diffraction lines corresponding to spaces "d" of 18.60, 5.21, 4.20, 4.01, 3.90 and 3.66 x 10"10 meters Furthermore, it is believed that a pigment of the formula (I) is new, where M is Ca, x is zero and is 1, in a red crystalline form that exhibits an X-ray diffraction pattern that has six prominent X-ray diffraction lines corresponding to the "d" spaces of 21.38, 13.31, 6.60, 5.35, 4.20, and 3.35 x 10"10 meters The pigments of the formula (I) can be prepared by lacquering, with a salt of magnesium, calcium, strontium, barium, or manganese, or a mixture of 2 or more of these salts, of a material of azo dye which can be obtained by coupling a diazonium salt of an amine of the formula: wherein Q is hydrogen, an alkali metal, or ammonium, and x and y are as defined hereinabove, with beta-hydroxynaphthoic acid (ABON). Examples of the salts which can be used to carry out the lagging are the chlorides, sulfates, nitrates, formates, and acetates of magnesium, calcium, strontium, barin, and manganese, and mixtures of two or more thereof. These metal salts for plating can be added to the pre-forged azo dye material. that is, after the coupling reaction, n can be included in the coupling reaction mixture, before coupling, together with the coupling component of beta-hydroxynaphthoic acid or more usually, together with the diazonium salt. The coupling and lacing reactions can be carried out using known procedures. In carrying out the coupling reaction, a solution or suspension of the diazonium salt can be added to a solution or suspension of the coupling component, or the solution or suspension of the coupling component can be added to the solution or suspension of the coupling component. diazonium salt, or both the diazonium salt solution or suspension and the coupling component solution or suspension can be added simultaneously to water, to an aqueous pH regulator, or to an aqueous solution of the metal salt used to effect the laced The pH of the coupling reaction mixture is preferably maintained. In the preparation of a pigment of the formula I wherein M is Ca, x is zero, and y is 1, when the coupling reaction is performed by the addition of a solution in suspension of the diazonium salt to a solution or suspension of coupling component, the pigment obtained on the coating of the resulting dye material with a calcium salt, is in the crystalline orange form previously described herein, while, when the coupling reaction is carried out by adding the solution or suspension of diazopium salt and the solution or suspension of coupling component simultaneously with water, an aqueous pH regulator, or an aqueous solution of a calcium salt of lacing , the pigment obtained on the lacquering is in the crystalline red form previously described herein. Conventional pigment additives may be included in the coupling reaction mixture, or it may be added to the azoic dye material before or after. laced These conventional additives include one or more surfactants to assist in the formation of separate particles, and to improve the properties of the finished product, and one or more resins, such as those conventionally used to form a resin pigment, and thereby improve dispersibility. of the pigment, being a typical resin of this type, a rosin, for example, a disproportionate rosin.

The pigment of the invention can be isolated by filtration from the reaction mixture, when the coupling and the lacquering are ignited. The filtered product can be washed with water to remove the soluble salts. The pigment can be dried and powdered by sieving, ball milling, spraying, or other known methods. In preferred embodiments, the high molecular weight material is a ter-oplastic resin, which may be a polyolefin such as polyethylene, polypropylene, or poly-isobutylene, polytetrafluoroethylene, a vinyl polymer such as polyvinyl chloride or polyvinyl acetate, polystyrene , an acrylic polymer such as "PMMA", a copolymer of styrene-butadiene, a copolymer of styrene-acrylonitrile, a copolymer of acrylonitrile-butadiene-styrene, a polyester such as polyethylene terephthalate or polybutylene terephthalate, a polya ida , a polyimide, a polycarbonate, a polyphenylene oxide, a polyether-ether-ketone resin (PEEK), a polyphenylene sulfide, or a polyether sulfone. In the especially preferred embodiments, the high molecular weight material is a polyolefin, especially a high density polyethylene. The pigmentation of the high molecular weight material can be done by mixing a pigment of the invention, if desired in the form of a master batch, with the substrate material, using a roller mill or other mixing or milling apparatus. The pigmented material can then be put into its desired shape by known processes, such as calendering, extrusion, centrifugation, compression molding, casting, or injection molding, to produce shaped plastic articles, such as films, sheets, fibers, ?? other articles configured particularly three-dimensional. The high pigmented molecular weight material generally contains from 0.001 to 30 parts, preferably from 0.1 to 5 parts by weight of the pigment, per 100 parts by weight of the material to be pigmented, although this amount can be varied depending on the depth of desired color. In order to obtain different shades of color, one or more fillers or other coloring components may be included, for example, white pigments, colored pigments. or black pigments, in the composition of the high molecular weight dp material, in addition to a pigment of the invention.

The invention is illustrated by the following examples in which the parts are by weight.

Example 1 To a dispersion of 4,6-dichloroanilin-2-sulfonic acid (12.1 grams) in water (80 milliliters), an aqueous solution is added to 47 percent sodium hydroxide (4.4 grams). The mixture is heated to 55 ° C, and stirred until a complete solution is obtained. The solution is cooled to 0 ° C by the addition of ice. A solution of sodium nitrite (3.5 grams) in water (50 milliliters) is added, followed by 36 percent aqueous hydrochloric acid (9.4 milliliters). The diazotized slurry obtained is stirred for 30 minutes, while the temperature is kept below 5CC. 2-Hydroxy-3-naphthoic acid (9.4 grams) is dissolved at 40 ° C in water (200 milliliters) and 47 percent aqueous sodium hydroxide (5.3 grams). The solution is cooled to 5 ° C by the addition of ice. Then the diazotized slurry is added, with stirring, for 18 minutes. The pH is maintained at 10.4-10.6 during the coupling, by the simultaneous addition of dilute aqueous sodium hydroxide. A solution of calcium chloride (8.7 grams) in water (50 milliliters) is added to the suspension obtained, and stirring is continued for 40 minutes, while maintaining a temperature of 8 to 10 ° C. Then the slurry heat at 95 ° C, and keep at this temperature for 60 minutes. The pH of the slurry is raised to 8.5 using dilute aqueous sodium hydroxide and a solution of Burez 9/18 - a disproportionate rosin modified with aleic acid - (2.3 grams) pn water, (80 milliliters), and 47 percent aqueous sodium hydroxide (0.7 grams) is added at 70 ° C. The pH of the resulting pigment slurry is adjusted to 7.2 by the addition of dilute hydrochloric acid, and the temperature is reduce to 70 ° C by adding ice. Then the slurry is filtered, and the tnrt of the obtained press is washed with water, dried at 70 ° C and calcined at 90 ° C. The resulting dry lumps are milled to give a pulverized pigment composition. Example 2 To a dispersion of 2-amino-4- (trifluoromethyl) benzenesulfonic acid (12.1 grams) in water (80 milliliters), a 47 percent aqueous solution of sodium hydroxide (4.4 grams) is added. The mixture is heated to 55 ° C, and stirred until a complete solution is obtained. The solution is cooled to 0 ° C by the addition of ice. A solution of sodium nitrite (3.5 grams) in water (50 milliliters) is added, followed by 36 percent aqueous hydrochloric acid (9.4 milliliters). The obtained diazotized slurry is stirred for 30 minutes while maintaining the temperature at <5 ° C. Dissolve 2-hydroxy-3-naphthoic acid at (9.6 grams) 40 ° C in water (200 milliliters) and 47 percent aqueous sodium hydroxide (5.3 grams). The solution is cooled to 5 ° C by the addition of ice. Then the diazotized slurry is added, with stirring, for 16 minutes. The pH is maintained at 10.4-10.6 during the coupling, by the simultaneous addition of dilute aqueous sodium hydroxide. A solution of calcium chloride (8.7 grams) in water (50 milliliters) is added to the suspension obtained, and stirring is continued for 25 minutes, while maintaining a temperature of 8 to 10 ° C.

Then the slurry is heated to 95 ° C, and kept at this temperature for 60 minutes. The pH of the slurry is raised to 8.5 using dilute aqueous sodium hydroxide and a solution of "Burez" 9/18 (2.2 grams) in water (80 milliliters), and 47 percent aqueous sodium hydroxide (0.7 grams) is added. ) at 70 ° C. The pH of the resulting pigment slurry is adjusted to 7.2 by the addition of dilute hydrochloric acid, and the temperature is reduced to 70 ° C by the addition of ice. The paste is then filtered, and the press cake obtained is washed with water, dried at 70 ° C, and calcined at 90 ° C. The resulting dry lumps are milled to give a pulverized pigment composition. The X-ray diffraction pattern of the resulting orange resin pigment powder, and that of the orange pigment obtained by an analogous procedure but omitting the rosin, has six prominent X-ray diffraction lines corresponding to the "d" spaces of 18.60, 5.21, 4.20, 4.01, 3.90, and 3.66 x IO "10 meters.

Example 3 High density polyethylene (100 parts) is mixed with the pigment of Example 1 (0.132 parts) and titanium dioxide (part 1). The mixture is milled in a two-roll mill, and then molded by injection. The resulting molding is stable to heat at 260 ° C for a residence time of 5 minutes, before a color change occurs, compared to a conventional mnl pp heated for 12 seconds at 200 ° C.

Example Example 3 is repeated, using the pigment of Example 2 (0.5 parts) instead of the pigment of Example t. The resulting molding is heat stable at 260 ° C for a residence time of 5 minutes, before a color change occurs, compared to a conventional molding heated for 12 seconds at 200 ° C.

Example 5 To a dispersion of 4,6-dimethylamine lin-2-sulfonic acid (10.0 grams) in water (150 milliliters) is added a 47 percent aqueous solution of sodium hydroxide (5.1 grams). The mixture is heated to 55 ° C, and stirred until a complete solution is obtained. The solution is cooled to 0 ° C by the addition of ice. A solution of sodium nitrite (3.5 grams) in water (25 milliliters) is added, followed by 36 percent aqueous hydrochloric acid (9.7 milliliters). The diazotized slurry obtained is stirred for 70 minutes while maintaining the temperature below 5 ° C. Just before coupling, solid calcium chloride (8.5 grams) is added. Dissolve 2-hydroxy-3-naphthoic acid (9.6 grams) at 40 ° C in water (200 milliliters) and 47 percent aqueous sodium hydroxide (5.1 grams). To this solution is added a solution of Portuguese Rosina WW - an abiethyl type resin - (4.2 grams), water (60 milliliters), and 47 percent aqueous sodium hydroxide (1.4 grams). The resulting solution is cooled to 6 ° C by the addition of ice. Then the diazotized slurry is added, with stirring, for 60 minutes. The pH SP maintained at 10.4-10.6 during coupling, by the simultaneous addition of dilute aqueous sodium hydroxide. The stirring SP continues for 60 minutes. Then the slurry is heated to 90 ° C, and the pH is adjusted to 7.2 by the addition of dilute hydrochloric acid. Then the temperature is reduced to 70 ° C by the addition of ice. The slurry is then filtered, and the final dp obtained in the press is washed with water, dried at 70 ° C, and calcined at 90 ° C. The resulting dry lumps are milled to give a pulverized pigment composition.

EXAMPLE 6 Example 3 is repeated, using the pigment of Example 5 (0.1 parts) in place of the pigment of Example 1. The resulting molding is heat stable at 280 ° C for a residence time of 5 minutes before it is present a camhin of color, comparing with a conventional molding heated for 12 seconds at 200 ° C.

Example 7 To a dispersion of 2-aminn-4- (trifluoromethyl) benzenesulfonic acid (24.1 grams) in water (250 milliliters), an aqueous solution is added to 47 percent sodium hydroxide (10.0 grams). The mixture is heated to 45 ° p, and stirred until a complete solution is obtained. Then add 36 percent aqueous hydrochloric acid (22.9 grams). The solution is cooled to 0 ° C by the addition of ice, and a solution of sodium nitrite (6.9 grams) in water (25 milliliters) is added. The obtained diazotized slurry is stirred for 30 minutes, while maintaining the temperature at <5 ° C. Just before coupling, a solution of calcium chloride (18.4 grams) in water (100 milliliters) is added. Dissolve 2-hydroxy-3-naphthoic acid (18.8 grams) at 35 ° C in water (250 milliliters) and 47 percent aqueous sodium hydroxide (10.0 grams). To this solution is added a solution of Portuguese Rosina WW - an abiethyl type resin - (4.3 grams), water (60 milliliters), and 47 percent aqueous sodium hydroxide (1.4 grams). The resulting solution is cooled to 5 ° C with the addition of ice. The diazotized slurry and the 2-hydroxy-3-phthalic acid / resin solution are then added simultaneously (for 55 minutes) to a vessel containing water (100 milliliters) at 5 ° C, with stirring. The pH is maintained at 10.4-10.6 during the coupling, by the simultaneous addition of dilute aqueous sodium hydroxide dp. The temperature is kept below 5 ° C by the periodic addition of ice. Stirring is continued for 30 minutes. The slurry is then heated to 90 ° C, and the pH is adjusted to 7.2 by the addition of dilute hydrochloric acid. Then the temperature is reduced to 70 ° C by the addition of ice. The slurry is then filtered, and the press cake obtained is washed with water, dried at 70 ° C, and calcined at 90 ° C. The resulting dry lumps are milled to give a pulverized pigment composition. The X-ray diffraction pattern of the powder of the resulting red pigment resin, and that of the red pigment obtained by an analogous procedure but omitting the resin, has six prominent X-ray diffraction lines corresponding to the "d" of 21.38, 13.31 , 6.60, 5.35, 4.20 and 3. 35 x IO "10 meters, EXAMPLE 8 Example 3 is repeated, using the pigment of Example 7 (0.1 parts) in place of the pigment of Example 1. The resulting molding is heat stable at 280 ° C for a residence time of 5 minutes, before it is present a color change, comparing with a conventional molding heated for 12 seconds at 200 ° C.

Claims (15)

1. A plastic composition comprising a high molecular weight material, and an effective coloring amount of an azo pigment of the formula: wherein M is Mg, Ca, Sr, Ba or Mn or a mixture of two or more thereof, R 1 and R 9 are chlorine or methyl, x is zero or 1, and is zero or 1 and the sum of x and y is 1, with the proviso that, when the high molecular weight material is polyvinyl chloride, and it is zero.

2. A composition according to claim 1, wherein M is Ca, x is 1, and y is zero.

3. A composition according to claim 1, wherein M is Ca, y is 1 and x is zero.

4. A composition according to claim 1, 2, or 3. wherein the pigment is in a resinated form.

5. A composition according to any of the preceding claims, wherein the high molecular weight material is a ter-oplastic resin.

6. A composition according to claim 5, wherein the thermoplastic resin is a polyolefin.

7. A composition according to claim 6, wherein the thermoplastic resin is high density polyethylene.

8. An azo pigment of the formula (I) as claimed in claim 1, wherein R I and R9 are each methyl, x is 1 e and is zero.

9. An azo pigment of formula (I) as claimed in claim 1, wherein M is Ca, x is zero, and y is 1, in a crystalline form exhibiting an X-ray diffraction pattern having six lines X-ray diffraction patterns that correspond to the spaces "d" of 18.60, 5.21, 4.20, 4.01, 3.90 and 3.66 x IO "10 meters

10. An azo pigment of the formula (I) as claimed in claim 1 , where M is Ca, x is zero, and y is 1, in a crystalline form that exhibits an X-ray diffraction pattern that has six prominent X-ray diffraction lines corresponding to the "d" spaces of 21.38, 13.31 , 6.60, 5.35, 4.20 and 3.35 x IO "10 meters.

11. A pigment according to claim 8, 9, or 10, in a resinated form.

12. A process for the preparation of a pigment according to claim 8, which comprises eplacar, with a salt of magnesium, calcium, strontium, barium, or manganese, or a mixture of two or more thereof, an azoic dye material which can be obtained by coupling a diazonium salt of an amine of the formula: (NH2 wherein Q is hydrogen, an alkali metal, or ammonium, i or R and R are each methyl, x is 1, and y is zero, with beta-hydroxynaphthoic acid.

13. A process according to claim 12, wherein the salt is a chloride, sulfate, nitrate, for- tate, or magnesium acetate, calcium, strontium, barium, or manganese, or a mixture of two or more thereof. .

14. A process for the preparation of a pigment according to claim 9, which comprises coupling a diazonium salt of an amine of the formula: wherein Q is hydrogen, an alkali metal, or ammonium, R1 and R2 are each methyl, x is zero and 1 is, with beta-hydroxynaphthoic acid, by the addition of a solution or suspension of the diazonium salt to a solution or suspension of the coupling component, and bonding the resulting dye material with a calcium salt.

15. A process for the preparation of a pigment according to claim 10, which comprises coupling a diazonium salt of an amine of the formula: wherein Q is hydrogen, an alkali metal, or ammonium, R1 and R2 are each methyl, x is zero, and y is 1, with beta-hydroxynaphthoic acid, by the addition of a solution or suspension of the diazonium salt, and a solution or suspension of the coupling component, simultaneously with water, an aqueous pH regulator, or an aqueous solution of a calcium-binding salt, and, wherein the solution or suspension of diazonium salt and the solution or suspension of the agent of coupling are simultaneously added to water or an aqueous pH regulator, bonding the resulting ink material with a calcium salt.